Azo dyestuffs of the pyrazolone series



Patented Apr. 30, 1946 .AZO DYESTUFFS OF THE PYRAZOLONE SERIES Eduard Moser, Riehen, Switzerland, assignor to Society of Chemical Industry in Basle, Basel, Switzerland, a Swiss firm No Drawing. Application March 6,1945, Serial No. 581,348. In Switzerland November 16, 1943 7 Claims. (Cl. 260-453) It has been found that the hitherto unknown heterocyclic compound the heterocyclic ring of azo-dyestuffs of the formula which is composed of three to four carbon atoms and three to two nitrogen atoms, the

S0311 s03H H are valuable dyestuffs. In this formula R1 stands groups ad c to being attached t Ca bo for the radical of a compound having a keto atoms'of the hetero-Tinggroup capable of undergoing enolization,Astands The value of these dyestuffs resides in their for an aromatic nucleus of the benzene series property of forming Valuable metallifel'ous @0111- wherein the group and the piexes with agents yielding metal, especially agents yielding copper, which dye textile mate- I rials, especially materials consisting of natural H r or regenerated cellulose or materials containing group stand in :4-position to each other and natural or regenerated cellulose, Valuable yellow which contains an atom grouping in ortho-posishades. The new dyestuffs are valuable because tion to the -N=N-- group capable of producing they possess an excellent affinity for the above complex m tal compounds with the atom groupmentioned materials, either as such or in the ing N=N,R'1, that is to say contains a arform of their alkali salts. By after-treating the boxyl group or a hydroxyl group, R2 stands for y materials with age yieldi g metal, espean aromatic radical having an atom grouping in 'cially with agents yielding copper, there are obortho positio t t group which is tained dyeings which are distinguished by their also capable of producing complex metal comlent f s p p ies, sp l y by their pounds in combination with the atom grouping excellent fastness to light, combined with an ex- N:N Py Py t d for th pymzolone 1111015115 cellent fastness to washing. In certain cases also of an 1-aryl-5-pyrazolone and as. stands for a the complex metal compounds produced in subconnecting member derived from a heterocyclic t ce may be direct dy g dye-Stuffs W ch compound having at least two mobile halogen produce dy i gs on the fiber which possess valuatoms, such as cyanuric chloride; able properties, especially an excellent fastness Among these dyestuffs those are particularly to light, without an after-treatment being necesvaluable which correspond in the free form to the mgeneral formula The new dyestuffs of the foregoing formula are V I (2H8 CH3 C=N o 0 OH l R-N=No-c 1 H H H 0 H S0311 S0311 wherein R stands for an aromatic nucleus of the made by methods known ,to be suitable for the benzene series which contains as substituent at manufacture of. such p o u r a p y least one substituent standing in ortho-position ouplin 1 mol of an'amino-azo y t fi 0f the to the N=N- group and. selected from the general formula group consising of the 0H and the COOH oups, R1 stands for a member of the group con- R1T-NN ANH2 sising or, hydrogen and aromatic nuclei of the wherein A stands for-an aromatic nucleus of the benzene series, and :1: stands for a connecting benzene series in which the N=l lgroup and link consisting of the radical of a, siX-membered the NHz-group stand in 1: 4-position to each wherein Py stands for the pyrazolone radical of a 1-aryl-5-pyrazolone and R2 stands for an arcmatic residue possessing an atom grouping in ortho-position to the -N=N- group which is capable of yielding complex metal compounds in combination with the atom grouping in known manner with the aid of heterocyclic compound of the kind of cyanuric chloride containing at least two mobile halogen atoms, and

esters, e. g., oxalacetic ester; or still other products, e. g., malonic acid derivatives or barbituric acid derivatives, e. g., barbituric acid itself, or finally also further products, e. g., benzoylacetone or dihydroxyquinoline.

As heterocyclic compounds containing at least two mobile halogen atoms from which the conif desired treating the resulting dyestuifs with agents yielding metal.

Dyestuffs of the same constitution are obtained by coupling a pyrazolone derivative of the general formula wherein an and Py have the above given significance and A stands for an aromatic nucleus of the benzene series in which the NHz-group and the NI-I group stand in 1:4-position to each other and which contains an atom grouping in ortho-position to the NHz-group which is capable of yielding complex metal compounds with the atom grouping -N=NR1 of the contemplated azo dyestuff, first with a diazotized aromatic amine which carries also in ortho-position to the diazo group such an atom grouping which is capable of yielding complex metal compounds in the formed azo-dyestufi in combination with the azo group and the pyrazolone grouping, then diazotizing the resulting dyestuff and coupling it with a keto group capable of undergoing enolization.

It isa-lso possible tostart from a dyestuif of the general formula l I 80311 SOiH wherein R1, A and R1! have the above given signiflcance, and couple this dyestufl, as indicated in the preceding paragraph, with a diazotized aromatic amine which contains in ortho-position to the diazo group such an atom grouping which is capable of yielding complex metal compounds in the resulting azo-dyestufi in combination with the azo group and the pyrazolone grouping.

As compounds containing keto groups capable of undergoing enolization there can be used, c. g., acetoacetic ester derivatives, such as arylides of acetoac'etic acid or pyrazolones obtained by condensing hydrazines with acetoacetic ester. Such pyrazolones are, e. g., 3-methyl- 5-pyrazolone and 1-phenyl-3-methyl-5-pyrazolone and derivatives thereof substituted in the benzene nucleus, e. g. by halogen atoms and sulfo groups. Further there can be used pyrazolones from other p-ketocarboxylic acid necting member x is derived, there can be used products such as cyanuric chloride, cyanuric bromide, 1 phenyl 3:5 dichlorotriazine, 1- methyl-3 5-dichlorotriazine, dichloroquinazollne, tribromopyrimidine and the like. When the linkage is complete any existing mobile halogen atoms can be exchanged by reaction with compounds, such as ammonia, primary amines, such as monomethylamine, monoethanolamine, aniline, 1 amino-d-hydroxybenzene-B-carboxy1ic acid, secondary amines, such as monomethylamiline and the like.

The diaz'o compound from aromatic amines which possess such an atom grouping in orthoposition to the amino group which in the finished azo dyestuif is capable of forming complex metal compounds in combination with the azo group and the pyrazolone grouping, is derived for example from compounds such as 1-hydroxy-2- aminobenzene, 1-hydroxy-2-amino-4-chloroben zene, 1-hydroxy-2-amino-4-nitrobenzene, l-hydroxy 2 amino-5-nitrobenzene, 1-hydroxy-2- amino-4:6- dinitrobenzene, 1-hydroxy-2-amino- 5-nitro-6-chlorobenzene, l-hydroxy-2-amino-4- methylbenzene, 1 hydroxy-2-amino-4-nitro-6- chlorobenzene, l-hydroxy-2-amine-4-nitrobenzene 6 sulfonic acid, l-hydroxy-2-amino- 6 nitrobenzene 4 sulfonic acid, l-hydroxy-2- aminobenzene-4-sulfamide, l-hydroxy-Z-aminonaphthalene-4:8-disulfonic acid, 2-hydroxy-laminonaphthalene-4-sulfonic acid, 2-hydroxy-1- amino-6-nitronaphthalene-4-sulfonic acid, 1- aminobenzene 2 carboxylic acid, l-aminolchlorobenzene 2 carboxylic acid, l-aminolnitro-benzene-2-carboxylic acid, especially however 1-amino-4-aroylaminobenzene-2-carboxylic acids, such as the products obtained by the action of aroylhalides, such as benzoylchloride, 4- chlorobenzoylchloride, 3-methoxy-benzoylchloride, benzoylchloride-3-sulfonic acid, naphthoic acid chloride, etc., on l-formylamino-l-aminobenzene-Z-carboxylic acid and subsequent saponification of the formyl group.

Among. the dyestufis of the present invention those are particularly valuable in which the radical R1 is the radical of a 5-pyrazolone, especially the radical of 3-methyl-5-pyrazolone. Further, it has been found in general that the new dyestuffs are particularly valuable if the atom groupings of the radicals A and R2 participating in the formation of complex metal compounds, are carboxyl groups. Reference has already been made to the 1-amino-4-aroylaminobenzene-2-carboxylic acid as starting material of the radical R2.

As already mentioned above, the new dyestuffs are distinguished by a pronounced afiinity for cellulose'or regenerated cellulose, for example for textiles consisting of or containing such materials, e. g., mixtures of cotton and artificial threads from regenerated cellulose, or regenerated cellulose delustred by inorganic pigments, or mixtures of wool and such artificial fibers. The new dyestuffs dye these materials preferably yellow to brown shades. The fastness to light and the wet fastness properties of the non-metallized dyestuffs can be essentially improved by aftertreatment with metal salts, especially copper salts. However, salts of other metals, such as cobalt, nickel, iron or chromium, can also be used. This metalliz ation can, be efiected simultaneously withdyei'ng. As has also already beenniene tioned, it may be appropriate in many cases, to produce the metal compounds of the dyestuffs as such and use the metalliferous products for example like substantive dyes. In this case the dyestuifs can be rhetallized in the course of their production, that is to say coupling can be carried out in the presence of agents yielding metal.

The following examples illustrate the invention, but are not to be regarded as limiting it in any way, the parts being by weight, unless stated otherwise;

Example 1 A solution of 45.1 parts of the pyrazolone of the formula at -5 C. A solution of 70 C. of 26.1 parts of the azo-dyestufi of the formula and 14 partsof caustic soda solution of 30 per cent. strengthin.800-partsof wateristhen added andthe temperature maintained for 2 hours. at 35-40 CI A solution. of parts of sodium bicarbonate in 30 parts of water, is thereupon introducedin drops andthe mixtureis further stirred for'4hours at the same temperature. '18

parts ofaniline are poured theretm-the whole is heated for 1 hour to 90-95 C., 5 gr'ofsodium carbonate are strewn in and the. condensation product is salted out. 47.3 partsthereof are dissolved in 600 parts of water, parts-of sodium carbonate-and a. little; ice are added and coupling isa'eflected with the following diazo component:

12:8 parts of 4-benzoylamino:-'l-aminobenzene- Z-carboxylic acid are dissolved in 140 parts of 5 Water and 7 parts of caustic soda solution of '10 is continued for 1 hour. The diazo compound has mainly precipitated.-When coupling is complete the dyestuff is satledout, filtered and dried. The dyestuff corresponds in the free form to the formula, l 3

and is a red brown powder dissolving in water or concentrated sulfuric acid to a brown solution.

The same dyestuff is obtained by coupling 35.9 parts of the azo-dyestufi from 4-benzoylamino-lamino-benzene z carboxylic acid and the pyrazolone of the Formula I with9i2 parts of cyanuric chloride at 0-5 C then further condensing with 13 parts of the azo dyestufi of the Formula II at 40 (3; and subsequentlystirring with 9 partsofaniline'for 1 hour-at -95 1). The dye- 5 stuff is then salted out, filtered and dried.

Similar dyestuffs are obtained when replacing the 18 parts of aniline in the .first paragraph of this'exarnple by 22 parts of meta-toluidine or mono-methylaniline. This reaction can also be carried out inter alia with ammonia, mono-ethylamine, mono-ethanolamine or diethylamine.

Example 2 61.6.parts of the dyestuff from diazotized 2- amino-1 -hydroxy-4-nitrobenzene and the pyrazolone ofthe Formula I of Example 1 are dissolved with 10.6 parts of sodium carbonate in 250 parts of water and the solution thus obtained is poured at 0-5" 0. into a suspension of 18.4 parts of cyanuric chloride in ice water. The hydrochloric acidwhichis liberated-isneutralized with. a solution of: 8;4' parts: of sodium bicarbonate in 30 parts: of waten A solution of 70 C. of 26.1 arts of the: azo-dyestuii of the Fo-rmula II of Example 1 and l 4 parts ofcaustic soda solution of 30- per cent; strengtlrin=800 parts of water is added and a solution o f 8.4-parts of sodium bicarbonate in 30 parts of water is then introduced in drops in the course of 2hou'rs. The whole is stirred for a further 4 hours at 35-40 0., 18 parts of-aniline are added and the mixture is heated for 1 hour to C. The finished dyestuff which corresponds in the free form to the formula is precipitated with common salt, filtered and dried. The dyeing on cotton which has been parts o! the after-treated with copper orange. A similar probable tormum J; N/ COOH (g Y Example 4 condensation product of the CHI dyestuif corresponding in the free form to the obtained according to Example 1 and 15 parts or formula sodium carbonate are dissolved in 600 cc. of water H 0... CH: J) V (J=N coon J: \NH

SOgH H is obtained when using 21.2 parts of 1-amino-2- and cooled to 0 C. with ice. To this solution is hydroxy 3:5:6 trichlorobenzene instead of 2- 30 added a diazo magma prepared in usual manner amino-l-hydroxyi-nitrobenzene. from 19 parts of 1-hydroxy-2-amino-4-nitro-6- Dyestuifs dyeing redder tints are obtained by chlorobenzene, parts of hydrochloric acid of using 1 amino-2-hydroxy 3-nitro-5-chlorobenper cent. strength and 3.5 parts of sodium nitrite.

zene or 1-amin0- -hy r Xy-3- The whole is stirred for several hours until couzene. v pling is complete, the dyestufl is salted out with Example 3 common salt, filtered and dried. It is a brown 67.8 parts of the dyestuff from 1-amino-4'-b'ropowder which corresponds in the free form to the mobenzene-2-carboxylic acid and the pyrazolone formula of the Formula I of Example 1 are condensed at which dissolves in water to a red brown solution With Parts Of cyanunc chlollde and in concentrated sulfuric acid to a yellow cording the s of i P fi anddthis brown solution. The 'dyeings produced with this mar con ensa ion pro no 15 en con ense a. c. with 26.1 parts of the dyestufi of the dyestufi 0n c0fl;OI111 and aiftertreated with copper Formula II of Example 1. The product is then 9? Ifiddlsh ye co heated f 1 hour to Q with 18 parts of aniline, Asimilar dyestuff is obtained when using 10.6 the dyestuif is salted out, filtered and dried. The Parts of obe new dycstufi corresponds in the free form to the z n n d of ydr0Xy-2-amino-4-nitro-6- formula p chlorobenzene.

, -H-N on. 00011 I v i 00011 N=NC=N\ v N \N J} NH B l N CHH NA i NON=N G -o A N 1 A t I N SOIH son 4 I H o a g p v v The on cotton which has been after-treat- Dyestufis dyeing considerably redder tints are gg gg g s g gggg fi aafi 20 obtained when using 7.7 parts of l-hydroxy-Z- parts of dichloroquinazolme instead of the amino-4-or 5-nitrobenzene as" diazotizlng comanuric chloride. 7 ponent.

Example 5 zene-5-carboxylic acid in 200 parts of water and 359 parts of the azmdyestufiiof the formula 14 parts of caustic soda solution of 30 percent.

L /NQOH=CH NH: II I i ll 1 SOaH S0311 0 H- H 0 1 o 0 on are dissolved with S-parts of sodium carbonate in strength is then added. The whole is heated to 500 parts of water and the solution is introduced 40 C., stirred for about two hours and a soluin drops at 0-5 C. to a, freshly prepared suspention of 8.4 parts of sodium bicarbonate in 60 parts sion of 9.2 parts of cyanuric chloride in ice water. 15 of water is added in drops. iter addition of 18 The hydrochloric acid which is liberated is neuparts of aniline the mixture is heated for 1 hour tralized within 1 hour with a solution of 4.2 parts to 90-100 C. i The condensation product of the of sodium bicarbonate in 20 parts of water. A probable formula 0 o s I r r OzN- N-C O -N OH=OH N I QI a Q Q H N H o-orn coon SOBH 303K 5 solution of 22.6 parts of the azo dyestuff of the is precipitated with 60 parts of hydrochloric acid formula v of per cent. strength and filtered. It is then CH3 30 dissolved with 18 parts of sodium carbonate in 800 parts of Water, a solution of 36 grams of crystallized sodium sulfide in 150 parts of water is (L added and the mixture is heated for 2 hours at .C o 6065 C., then acidified with hydrochloric acid I of 30 per cent. strength and filtered. For the (1003 purpose of purification the amino product is dis- 5 solved inlOOO parts of Water and sodium car- With 10.6 parts of sodium carbonate in 400 parts bonate, filtered from sulfur and again isolated by of water is added and the temperature is mainacidifying with hydrochloric acid.

tained for 2 hours at 35-4-0" C. A solution of 4.2 40 38.5 "pa1"ts of this product are dissolved with parts of sodium bicarbonate in 20 parts of water 20 parts of sodium carbonate in 400 parts of is then added in drops and stirring is continued Water, cooled with ice' to 5 C. and added to a for 4 hours at the same temperature. After addiazo solution prepared in known manner from dition of 9 parts of aniline the whole is heated for 12.8 parts of 1-amin0- l-benzoylamino-benzene- 1 hour to 90-95 0., 5 parts of sodium carbonate Z-carboxylic acid. Stirring is continued until couare strewn in and the dyestuff is precipitated pling is complete. The aminoazo dyestuff is prewith common salt, filtered and dried. The dyecipitated by addition of common salt and filtered. stuff corresponding in the free form to the Itis dissolved in 400 parts of hot Water, 3.5 parts formula of sodium nitrite are added and the whole is is a brownpowder dissolving in water or con- 6 poured to a mixture of ice and 32 parts of hydrocentrated sulfuric acid to a brown solution, the chloric acid of 30 per cent. strength, cooled to dyeings of which on cotton after-treated with 10-15 C, The diazotization is complete after 2 copper being of reddish yellow color. hours. The diazo magma is poured into a cooled L solution of 5 parts of3-methyl-5-pyrazolone and Example 6 20 parts of sodium carbonate in 80 parts of Water and the whole is stirred for several hours. The dyestuff which has precipitated is then filtered and dried. It is identical with the dyestuif obtained according to Example 1.

' A solutionof 45.1 parts of 4-aminostilbene 2 2"-disulfonic acid-4- 3 -methyl-5-pyrazolone] and 10.6 parts of sodium carbonate in 250 parts of water is added, while thoroughly stirringat 0-5 (2., to a freshly prepared suspension of 18.4 parts Example 7 of cyanuric chloride in ice water. The hydrochloric acid which is liberated is neutralized in 35.9 parts of the aminoazo dyestuff of the first the course of two hours with a solution of 8.4 formula of Example'5 are dissolved with 8 parts parts of sodium bicarbonate in 60 parts. of water. of sodium carbonate in 500 parts of water and A solution of 18.2 parts of 1-amino-4-nitrobenthe solution is added in drops at O-5 C. to a fresh- [prepared from 15.4 parts of diazotized l-amino- SOIH 2-hydroxy-4-nitrobenzene and 28.8 parts of l- (2'-chloro-5'-sulfo) -phenyl 3-methyl-5-pyrazolone and subsequent reduction with 36 parts of crystallized sodium sulfide for 2 hours at 60-65" 0.] and 5.3 parts of sodium carbonate in 400 parts of water is added and the temperature'is maintained for 2 hours at 3540 C. A solution of 4.2 parts of sodium bicarbonate in 30 parts of water is then added in drops and stirring is continued for 4 hours at 40 C. After addition of 9 parts of aniline the mixture is heated for 1 hour to 90-95 0., parts of sodium carbonate are strewn in and the dyestufi is precipitated with common salt, filtered and dried. The dyestufl. corresponding in the free form to the formula crystallized copper sulfate and 2.5 parts of tartaric acid in 100 parts of water neutralized with caustic soda solution is then added tothe dyebath and the cotton is treated during hour at about 95 0., then rinsed in the usual manner and dried. It is dyed fast yellow shades.

As already mentioned in the specification, the dyestuffs of this invention can also be used for dyeing mixed fabrics, such as for example mixtures of wool and viscose staple fiber. In such cases dyeing can be effected in a neutral bath in the presence of sodium chromate or potassium chromate.

What I claim is:

1. The dyestufis corresponding in the free form to the general formula wherein R. stands for an aromatic nucleus of the benzene series which contains as substituent at least one substituent standing in ortho-position to the N=N group and selected from the group consisting of the OH and the COOH- groups, R1 stands for a member of the group consisting of hydrogen and aromatic nuclei of the benzene series, and It: stands for a connecting link consisting of the radical of a six-membered heterocyclic compound the heterocylic ring of which is composed of three to four carbon atoms and three to two nitrogen atoms, the

. I t groups adjacent to a: being attached to carbon atoms of the hetero-ring.

is a. brown powder dissolving in water to a redbrown solution, in concentrated sulfuric acid to a yellow brown solution, the dyeings of which on cotton after-treated with copper being of reddish yellow color.

Example 8 100 parts of cotton are introduced at 40-50 C. into a dyebath consisting of 3000 parts of water, 1.5 parts of dyestufi prepared according to the first part of Example 1 and 2 parts of sodium carbonate. The bath is heated to 90-95 0. within V2 hour, 30 parts of crystallized sodium sulfate are added and dyeing is continued at this tem- 2. The dyestuffs corresponding in the free form to the general formula C COOH I I H H O SOQH perature for hour. A solution of 2 parts of the benzene series.

3. The dyestuffs corresponding in the free form wherein R stands for an aromatic nucleus of the to the general formula benzene series which contains as substituent at wherein R stands for an aromatic nucleus of the least one substituent standing in ortho-position benzene series which contains as substituent at to the N=N- group and selected from the least one substituent standing in ortho-position group consisting of the 01-1- and the COOH- to the --N=N-- group and selected from the groupsgroup consisting of the OH-- and COOI-L- 5. The dyestuif corresponding in the free form groups, Ra stands for a member selected from the to the formula OaH group consisting of hydrogen and alkyl, and R4 6. The dystufi: corresponding in the free form stands for a member selected from the group conto the formula W w an a C C C H a H N O O C TH NIO N c N H N w K N m 0 S H C H C a. 0 S N N o H CIICIIJV a N sisting of hydrogen, alkyl and aryl nuclei of the 7. The dyestuff corresponding in the free form benzene series. to the formula OH=CH SOIH CH=CH SOaH EDUARD MOSER. 

